Cycloheptatrienyl vanadium tricarbonyl



, dium tricarbonyl compounds.

.tion is preparation of United States Patent 3,264,334 Patented August 2, 1966 ice 3,264,334 CYCLOHEPTATRIENYL VANADIUM TRICARBONYL Robert P. M. Werner Binuinge'n,Basel-Laud, Switzerland, asslgnor to Ethyl CbrporationQNeWYOrk, N.Y., acorporation of Virginia A N0 Drawing. Filed Apr. 23, 1962, Ser. No. 189,293

2 Claims. (Cl. 260-429) pounds.

compounds. nomical method of plating vanadium. Other objects.

following discussion and claims.

This inventioncomprises cycloheptatrienyl vanadium tricarbonyl compounds. These compounds can ,b'efrepresented by the formula wherein Q is a cycl-oheptatrienyl radical having. from 7 to about 15 carbon atoms.

The compounds of this invention are prepared by a process which comprises reacting vanadium hexacarbonyl with an organic cycloheptatriene compound. The cycloheptatriene compounds employed .do not contain. any metallic constituents. It has been found thatthis preparation ..may.. be accomplished .in a system wherethe only .reactants are vanadium hexacarbonyl and the organic compound. However, in some. instances a non-reactive solvent .is efficaciously employed.

process of this In. general, tem- C. are employed.

The temperatures employed in the invention may vary over a wide range. peratures of from about 45 C. to 300 .However, a. preferred temperature range is from 50 C.

to 165 C. as reactions conducted inthis range'lead to a high yield of products with a minimum of undesirable side reactions. Reaction times of from 10 minutes to 10 hours. or longerrnay be employed. Ordinarily, heating .periodsof from 15 minutes to 7 hours are sufficient to produce a good yield of product. It is preferred that the temperature and the reaction time are compatible with the products and the reactants.

Cycloheptatriene is a conjugated cyclic hydrocarbon having SIcarbon-to-carbon double bonds ,in a-7-carbon atom ring. 'The compound has the. formula CqHg. It can be represented by the following formula:

The cycloheptatriene compound .whichis a reactant in the process'of this invention canbe selected from a wide range of cycloheptatriene organic compounds.

.Any or all of the carbon atoms in theabove formula may be substituted ,by monovaleintradicals containing from one to about eight carbon atoms. Typical monovalent radicals are alkyl, aryl, cycloalkyl, alkenyl, cycloalkenyl, aralkyl and alkaryl radicals. Examples of these radicals are the 'methyhpropyl, phenyl, tert-butyl, pchlorophenyl, neo -pentyl, .chlonomethyl, octyl, cyclohexyl,

' the appropriate boiling range.

b on atoms.

"ployed in excess.

: hex'aethyldisiloxane,

pyldiphenyldi 'silane and the like.

propenyl, cyclopentyl, cyclopentenyl, cyclopropyl, 2- methyI-Z-butenyl, cyclohexenyl, benzyl, 2-phenylethyl, pethylphenyl, .2,4-di methylphenyl and tolyl radicals.

Preferred substituent groups are monovalent hydrocarbon groups conta-iningfr-om one 'to about seven car- I I Itjis further preferred that the sum ofthe carbon atoms in all of the substituent groups does not exceed ten. .When this preference is satisfied, the compounds are more readily available.

.The applicable cycloheptatriene compounds include, for example, cycloheptatrien'e, l-cycloheptatrienyl cycloheptatriene, 1 methylcycloheptatriene, 2-iso'propylcyclohep tatr iene, 1,4-diethylcyclohept'atriene, 4-phenylcyclohep- .tatriene, 3 decyl-cycloheptatriene, pl-tert-butylcycloheptatriene, 1,3 diisopropylcycloheptatriene', 'lj-hydro'xycycid heptatriene, l cycloheptatrienyl' carboxylic j acid propylester, S-cyclOheptatrienyl butylether, 2-N-ethylcycloheptatrienyl amine, 1-methylaminocycloheptatriene, l-chlorocycloheptatriene, 3,5-d-i methoxycycloheptatriene, l-dimethoxymethylcycloheptatriene, 3 sopropyl l-phenylcycloheptatriene, l methyl-4-phenylcycloheptatriene, 3- hydroxymethyicycloheptatriene, 1cycloheptatriene carboxylic acid, l-cycloheptatriene and 'the like. Those compounds composed entirely of carbon and hydrogen'and having up to about 14 oarbon atoms are preferred since they lead to more easily recoverable products and constitute the most readily available'cycloheptatriene compounds.

'Whereas the process of the present invention can be conducted at atmospheric pressureat the reflux temperature of the system, higher or lower temperatures and higher pressures may also'be conveniently employed. In certain instances, 'it is desirable't-o conduct the reaction in the vapor phase bypassingthe vapor of the cycloheptatriene compound over the metal carbonyl in a hot tube. When the reaction is conducted at super-atmospheric pressure, temperatures of from C. to 250 C. are

preferred although temper'atures'outside this range may also beemp-loyed. Since carbon monoxide is a product of this reaction, and an excess of carbon monoxide pressure may inhibit further formation of'the' desired compound, it is advantageous to allow the excess carbon monoxide to escape from the reaction vessel.

No solvent is required in conducting the process of this invention if the cycloheptatriene compound is em- However, it is often convenient to employ an inert solvent. The solvent aifordsa homogeuous reaction mixture and prevent local superheating and consequent destruction of the vcycloheptatriene compound.

Satura-ted hydrocarbons are the preferred solvents. Other solvents which can be employed include ethers, aliphatic esters, silicone oils, aliphatic polyesters, and other liquids inert to the primary reactants andproducts. Examples of "the compounds usable as's'olvents in" the process of this invention include n-octane, n-nonane, n-decane and the various iso-decanes and other paraflinic hydrocarbons having up to about 20 caijbon atoms, such as eicosane, octadecane, pentadecane and the like. Ether solvents which may be employed include ethyloctylether, amyl ethyl ether, ethyl heptylether and ethyl hexylet-her. Ester solvents which may be employed include pentyl 2- methylpropanoate, pentylbutanoate, butyl butanoate, 'y methylbutyl butanoate, ethyl decanoate, methyl decano ate, pentyl hexanoate, ethyl hexanoate and thelike. Applicable silicone oils include copblymers and homopolymers of the various organosiloxanes and organosilanes having Examples of these are the dimethyl polysiloxanes, methylphenyl polysiloxanes, diphenyl polysiloxanes, diQchlorophenyl) polysiloxanes,

hexapropyl disilane, diethyldipro- The polyesters applicapletely esterified dicarboxylic acids.

3 ble as solvents in the process of this invention are comw Esters may be employed derived from succinic, maleic, pyrotartaric, glutaric, adipic, .pimelic, suberic,.azelaic, sebacic and pinic pounds prepared by the process of this invention can be recovered by evaporation of the excess cycloheptatriene reactant and solvent. The compounds may be purified by recrystallization from solvents such as hydrocarbons or lower aliphatic ethers.

The tollowingexamples, in which all parts and per-:-

centagesare by weight, are illustrative of the compounds of this invention and the process for their preparation EXAMPLE I A mixture comprising 8.5 parts of vanadium hexacarbonyl, 18.4 partsof cycloheptatriene and 240 parts of n-hexane was stirred and heated at reflux (63 to 68 C.) for one hour under nitrogen. During this time,-a large quantity of gas was evolved. The reaction mixture was then filtered while warm, using filter aid, under nitrogen, to give a green solution and a fine brownish precipi-' tate which was washed several times with n-hexane. The

green solution, including the washings, was reducedin volume under vacuum to about 25-30 ml., and on cool:

ing in a dry ice acetone bath, shiny, brown black crystals were obtained. After two recrystallizations of the'crystals from n-hexane, 1.9 parts of crystalline productwas obtained. The moderately stable compound melted at 134-137 0., could be sublirned at 4080 C. under vacuum and was found to be diamagnetic. On analysis there was found: C, 53.0; H, 3.44; V, 22.5. Calculated for C H VO C, 53.12; H, 3.12; V, 22.54 percent. The molecular weight as determined by the Signermethd was found to .be 220. That calculated for C H VO cycloheptatrienyl vanadium tricarbonyl, was 226.11. On the basis of the above analytical data and nuclear magnetic resonance data, the compound was unequivocally established as cycloheptatrienyl vanadium tricarbonyl.

EXAMPLE II The procedure of Example I is followed except that EXAMPLE III When methyl cycloheptatriene is substituted for the cycloheptatriene in Example I, the product is methylcycloheptatrienyl vanadium tricarbonyl.

EXAMPLE IV When theprocedure of Example I is followedexcept The product is octyl I that chloromethylcycloheptatriene is used as the reactant and ligroin as the solvent, the cycloheptatrienyl vanadium tricarbonyl.

EXAMPLE V The procedure of Example I is followed except that 2,4-diethylphenyl cycloheptatriene is used as the reactant and n-hexane as the solvent. 1 The product is 2,4-diethylphenyl cycloheptatrienyl vanadium tricarbonyl.

EXAMPLE VI Trimethyl cycloheptatriene dissolved in n-nonane yields trimethylcycloheptatrienyl vanadium tricarbonyl when the procedure-of Example I is followed.

product is chloromethyl- EXAMPLE VII The .apparatusconsists of a vessel equipped with heating means and a conduit for passing'vapor into a thermal reactor tube which is also equipped with heating means. A cold trap for isolating reaction products is located downstream from the thermal reactor tube. The vessel is charged with a quantity o'fcycloheptatriene and the reactor tube is charged with,vanadiurnhexacarbonyl. The. systernis flushed with nitrogen and the. continuous flow of nitrogen is maintained above thecycloheptatriene to carrythe cycloheptatrienevapor over the vanadium hexacarbonylin the reactor tube. The reactor tube is heated andmaintained at-about 140 C. The cyclo heptatriene is heatedtothe-boiling point and thecycloheptatriene vapor is carried over the. vanadium hexacarbonyl and contacted therewith. Cycloheptatrienyl vanadiumtricarbonyl is isolatedinthe cold trap.-

EXAMPLE vnr Vapor phase-plating of a steel with cycloheptatrienyl vanadium tricarbonyl A suitable quantity. of cycloheptatrienyl. vanadium,

tricarbonyl is placed into a .reservoirequipped with heating means. The reservoir-is connected through avalve,

to a plating chamberwhereinthe object tobe plated, a steel plate, is supported. The steel plate is connected .to a The plating chamber is I equipped with an induction coil which. surrounds the.-

temperature .measuring :device.

metal object to be: plated. The .plating chamber is connected to a cold trap downstream from the. reservoir and I- the cold trap :is connected to a vacuumpump. x The system is evacuated to a pressure less than 0.2 mm. of mercury. The reservoir issufliciently heated to volatilize the deposit using this technique... Iron, cooper, bronze, brass, chromium and various porcelains and othercerarnics can be coated.

As mentioned previously, antobject'of' this invention is to provide an improved method for plating vanadium on a variety. of substrates- A'further object is. toprovide a more eflicient and effective method for plating vanadium in an economical manner.

The above :and other objects are accomplished by a process for plating vanadium metal upon a substrate which comprises thermally decomposing :a vapor consisting essentially of a 'cycloheptatrienylvanadium tricarbonyl in contact with said substrate wherein said process is conducted=at a temperature of from about 200 C to about 600 C., and at a pressure of from about 0.01 l mm. to about mm. of mercury; The objects set out I hereinabove are further accomplished bya process for plating vanadium on a substrate which comprises heating said substrate toa temperature of between about:200 to about 500 sentially of one C. C; and contacting a vapor consisting esof thetcompounds prepared by the process of this invention with said substrate wherein :said contactmg is carried out at-a pressure of between about 0.01"

mm. to about 10 mm. of mercury.

Thedeposition chamber pressure may range from about 0.001 mm; of mercury to about 30 mm. of mercury. The preferred pressure in .the deposition chamber is from about:0.01 to about 10 111111201 mercury since better plates are-obtained within this pressure range and vtr'ansportation'of the plating vapor is facilitated. The most preferred pressure range is from about 0.01 to about 0.5 mm. of mercury since better results are obtained within this range.

The temperature conditions coupled with pressure in the plating chamber forms the critical feature of the present process. Thus, where the temperature ranges from about 200 C. to about 600 0., preferably 400 C. to 550 C., and the pressure in the chamber ranges from about 0.01 to about mm. of mercury, better plates are obtained having better adherence to the substrate and pinhole free surfaces.

In the process of this invention a carrier gas is not required or desirable. Generally carrier gases tend to react with the vanadium being plated to form carbides, nitrides or other products as the metal is deposited upon the substrate. Furthermore, carrier gases usually contain small amounts of impurities which ultimately affect the plating process. Hence, a carrier gas is not generally used in the process of this invention and is preferably avoided. However, under some circumstances, because of the more improved plates obtained by the unique combination of temperature and pressure conditions of this invention, carrier gases such as hydrogen, carbon dioxide, nitrogen and argon may be tolerated and used to facilitate the flow of the vaporized plating compound.

In initially vaporizing the plating compound prior to its use in the actual plating operation, temperatures from about 80 C. to about 200 C. may be used. It is preferred, however, to vaporize the cycloheptatrienyl vanadium tricarbonyl compound at temperatures from about 125 C. to about 200 C. The temperature used depends on the flow rate desired.

The flow rate of the vapor is dependent to a certain extent upon the amount of pressure in the plating chamber and the temperature to which the compound is subjected. Ordinarily, the flow rates of the plating compound employed vary from about 1 foot per minute to about 30 feet per second although faster or slower rates can be employed.

The time required to plate vanadium by the process of this invention varies over a wide range, depending on flow rate, desired coating thickness, deposition chamber pressure, temperature of the substrate and the vaporization temperature of the plating compound. However, times from about minutes to about 10 hours are generally acceptable. For economic reasons, it is preferred, 'however, that the process time range from about 30 minutes to about 3 hours, depending on the desired thickness of the vanadium coating desired.

Adherent vanadium coatings can be obtained through depositing its vapor directly upon any substrate that can withstand the plating conditions. Typical examples of substrates which may be plated are nickel, pyrex glass, beryllium, molybdenum, graphite, ceramics, high temperature resistant plastics, and the like. The preferred substrates which can be plated are porcelains, nickel, ferrous metal substrates, aluminum and the like.

-In some cases, the substrate to be plated is preferably subjected to initial preparation. This is especially true in the case of metal substrates. In other words, the degree of adherence achieved through the unique vapor plating process of this invention, in some instances where desirable, can be further improved by an appropriate metal surface pre-treatment. The best metal surface preparation is achieved through degreasing With a solvent such as 1,1,2-trichloroethylene or the like followed by light sand blasting. The vapor plated coatings have better adherence on slightly uneven surfaces, such as created by sandblasting, than on highly polished substrates. Thus, not desiring to be bound by theoretical considerations, it is felt that sandblasting permits a better anchoring effect of the deposited metal which penetrates into the small pits of the surface. On substrates such as graphite and ceramics where the surface is already nonuniform, if desired, degreasing can be performed to assure a clean plating surface. Other substrate pre-treatments known to the art can be employed, if desired, and will now be evident for the above and other substrates.

The types of apparatus which may be used for the plating operation are any of the apparatus described in the prior art, such as set forth by Lander and Germer in Plating Molybdenum, Tungsten and Chromium by Thermal deposition of Their Carbonyls, or by Powell, Campbell and Gonser in the book Vapor Plating, John Wiley & Sons, New York, 1955, wherein a vacuum chamber is used.

Heating may be achieved by numerous methods. Generally, resistance heating, infrared heating or induction heating are used according to the nature of the substrate and the type of equipment which is employed since the equipment largely determines the heat requirements. Flat samples such as metal plates can generally be heated by resistance heating apparatus such as a hot plate. For uneven shaped objects, induction heating or infrared heating may be used, depending on the nature of the substrate.

For the plating operation of this invention, the object to be plated is heated to a temperature of 250 to 550 C. preferably 300 to 450 C. in an enclosed chamber. The system is evacuated and the plating agent is heated to an appropriate temperature wherein it possesses vapor pressure of preferably up to about 5 mm. of mercury. In most instances, the process is conducted at no lower than 0.01 mm. mercury pressure. The vapors of the plating agent are pulled through the system as the vacuum pump operates, and they impinge on the heated object, decomposing and forming the metallic coating.

In addition to the thermal decomposition techniques discussed hereinabove for decomposing the plating agents of this invention, other methods for decomposition can be employed. Such methods are decomposition of the vanadium compound of this invention by ultrasonic frequency or by ultraviolet irradiation. The former process involves essentially the same procedure as employed in Example VII-I With the exception that an ultrasonic generator is proximately positioned to the plating apparatus. The vanadium compound is then heated to its decomposition threshold and thereafter the ultrasonic generator is utilized to effect final decomposition. Decomposition by ultraviolet irradiation involves essentially the same method as utilized in Example VIII with the exception that in place of the resistance furnace there is utilized for heating a battery of ultraviolet and infrared lamps placed circumferentially around the outside of the heating chamber. The substrate to be heated is brought to a temperature just below the decomposition temperature of the vanadium compound with the infrared heating and thereafter decomposition is effected with ultraviolet rays.

Although the above techniques generally employ the vanadium plating agent in its vapor phase, other techniques besides vapor phase plating can be employed. For example, the substrate to be plated can be placed in a decomposition chamber and the plating agent packed in contact with the element and thereafter heated to a temperature above the decomposition temperature of the plating agent. The volatile "by-products of the decomposition reaction escape leaving an adherent deposit on the substrate.

Deposition of metal on a glass cloth illustrates the latter process. A glass cloth band weighing one gram is dried for one hour in an oven at C. It is then placed in a tube which is devoid of air and there is added to the tube 0.5 gram of cycloheptatrienyl vanadium tricarbonyl. The tube is heated at 400 C. for one hour after which time the tube is cooled and opened. The cloth has a uniform metallic grey appearance and exhibits a gain in Weight. The cloth has greatly decreased resistivity. An application of current to the cloth causes an increase in its temperature. Thus, a conducting cloth is prepared. This cloth can be used to reduce static electricity, for

' decoration, for thermal insulation by reflection, and as a heating element.

The, novel compounds of :this invention are particu:

, larly useful as chemical intermediates, fuel and lubricating oil additives, polymerization catalysts, combustion con-v trol additives, fungicides, herbicides, pesticides and baatericides.

Having fully defined the novel compounds of this in-,

vention, their mode of preparation and their utility, I

, 8 I wherein Q is :a ,cycloheptatrienyl radical having from '7 to about 15 carbonatoms.

2. Cyclohept atrienylvanadium tricarbonyl.

References Cited by thexExaminer UNITED STATES PATENTS 2,818,416 12/1957 BroWn.-.

MURRAYKATZ, Primal Examiner.-

15 RICHARD .DL- NEV'IUS, Examiner.

R. E. HOWARD, A. GOLIAN; Assistaut Examiners; 

1. CYCLOHEPTARIENTYL VANADIUM TRICARBONYL COMPOUNDS HAVING THE FORMULA 